High-speed quenching composition



United States Patent 3,150,510 HIGH-SPEED QUENCEHNG CQMEQSTTION Irving Rozalsiry, East Alton, and Curtis L. Early, Aiton, 12., assignors to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 23, 1962, Ser. No. 175,339 Ciaims. (Cl. 148-29) This invention relates to improved high-speed quenching oil compositions for use in the metallurgical industries and to the method of quenching metals therewith.

In the process of hardening metals such as steel, it is common practice to use as the quenching medium water, oil or compressed air, according to the type of steel. Recently salts or aqueous solutions of salts have also been used for this purpose, but these have the disadvantage that they solidify or deposit solids on cooling to room temperature. Fatty oils,.especially rapeseed oil, are used as quenching oils, but these have been gradually superseded by mineral quenching oils. It has also been proposed to harden and temper steels using baths containing naphthalene monoor disulfonic acids or salts thereof or anthracene monoor disulfonic acids or salts thereof. Sulfonic acids or their salts are mixed with water or oil to form the treating bath and the oils generally used are linseed oil, cotton seed oil and other fatty substances.

Quenching compositions of the above types are defec tive in a number of respects among which are that water or emulsion quenching causes stress and strains in the metal such as steel which results in warping and cracking thereof, rendering the metal unusable. Oil quenching, although essential obviating this objectionable characteristic of water or emulsion quenching compositions, tend to leave adherent deposits on quenched metal surfaces which must be removed by relatively expensive buiiing or machining operations prior to further processing of the metal. This, plus the fact that oil quenching is expensive and the life of such oil is short because of thermal and oxidation deterioration, thereby requiring continuous replacement with fresh oils, presents a pressing problem to the industry.

An object of the present invention is an improved process for quenching metals. A further object is to provide a quenching oil composition of superior speed and stability. Another object is to provide a q enching oil composition capable of producing bright quenched metal surfaces. 1 Still other objects will be apparent from the following description of the invention.

The above objects may be attained in accordance with the present invention by quenching a metal in a thermally and oxidatively stable mixture of particular petroleum fractions which contains a critical amount Within the range of from about 0.1% to about 2%, preferably between 0.2% and 0.5% by weight each of an additive mixture comprising (A) a non-ash forming oil-soluble N-C acyl sarcosine and nitrogen-base salts or esters thereof and (B) an oil-soluble alkali or alkalineearth metal petroleum sulfonates.

By the particular petroleummixture is meant a blend of 50-95% (preferably 60-70%) of (1 a mineral oil fraction in the viscosity range of 80-250 SUS at 100 F., a viscosity index of at least 90, preferably between 95 and 120 and an aromatic content of atleast preferably between 30 and 60%, such as a 100 SUS at 100? F. HVI neutral or 250 SUS at 100 F. I-IVI neutral and the balance of the blend being (2) a highly refinedmedium VI (70-80 VI) light mineral oil such as a spray base oil or transformer oil in the viscosity range of from 40-100 SUS at 100 F. and/ or a heavy residue fractionsuch as a 150-210 bright stock or an asphalt or derivatives thereof.

The surprising discovery made resides in the, fact that both the mineral oil blend and the additive mixture of the Patented Dec. 1, 1964 present invention exert a profound eifect on both the quenching speed and surface brightness of the metal being treated. Thus using a conventional or ordinary quenching oil such as described in US. Patents 2,866,729, 2,485,103 or 2,340,724 with the additives of the present invention taken singly or in combination results in poor quick-quenching and only fair surface brightness.

The first additive (A) namely NC acyl sarcosines and derivatives thereof have the general Formula I RC ON-CHg-C 0 OX where R is a (3 0 saturated or unsaturated alkyl radical, preferably a C1344 unsaturated alkyl radical, and X is the same as R or is a hydrogen or is an amine, preferably a heterocyclic amine. Thus R may be decyl, tetradecyl, dodecyl, tetradecenyl, hexadecenyl, oleyl, ricinoleyl radicals and the amine may be a C2043 alkyl amine such as monoor didecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and octadeccnyl amines; heterocyclic amines such as substituted imidazolines having the Formula II where R is the same as R in Formula I. Examples of N- acyl sarcosines used as quenching speed additive and surface brighteners are illustrated by the following: N-lauroyl sarcosine, N-stearoyl sarcosine, N-caproyl sarcosine, N-myristol sarcosine, N-oleoyl sarcosine, N-palmitoyl sarcosine, and N-archidoyl sarcosine, amine salts of such acid as monodecylamine, didecylamine, monotetradecylamine, ditetradecylamine, monoctadecylamine, dioctadecylamine, 1-hydroxyethyl-2-undecylimidazoline, l-hydroxyethyl 2 heptadecylimidazoline and 1 hydroxycthyl 2- heptadecylirnidazoline salts of N-lauroyl sarcosine or N- cocoyl or N-oleoyl sarcosine or N-stearyl sarcosine, particularly preferred compounds are the free acids such as N-oleoyl sarcosine, o'ctadec'ylamine salts of N-oleoyl sarcosine and 1-hydroxyethyl-2-heptadecenyl imidazoline salt of N-oleoyl sarcosine. The esters include the N-C 'acyl sarcosinates of C alkanols such as octyl, decyl, dodecyl and octadecyl'alcohols, e.g., N-o-leoyl sarcosinate of octyl alcohol, N-oleoyl sarcosinate of octadecyl alcohol. Mixtures of the free acid, ester or amine salts may be used such as a mixture of N-oleoyl sarcosine and l-hydroxyethyl-2-heptadecenyl imidazoline salt of N- oleoyl sarcosine.

The other essential additive (B) is an oil-soluble alkali metal and/or aikaline earth petroleum sulfonate. These sulfonates are well. known in the art and are prepared by reacting a mineral oil withconcentrated or fuming sulfuric acid to form oil-soluble sulfonic acids which are then recovered by treatment with an alkali metal base such as sodium hydroxide or potassium hydroxide or with calcium or barium hydrox de or carbonates followed by extraction. These oil-soluble soaps are available as 30% to 70% concentrates in mineral oil.

Although sulfonates are known quenching oil additives because of their ability to improve the speed of quenchinvention must have thermal and oxidative resistant properties capable of meeting the requirements desired in a quenching oil. Thus the oil of part (1) of the blend must be high viscosity index oil (-120 VI) in the viscosity range of 80-250 SUS at F., preferably 100-150 SUS at 100 F. and an aromatic content of 15-60%. Such oils 3 may be illustrated by a HVI 100 neutral having the following properties (Ia):

Gr.,API 31.6 Color, NPA ;+1 Flash, F. 370 Pour point, F. Viscosity at 100 F., SUS 103 Viscosity index 90 Aromatic, percent 15.5 Naphthenes, percent 68.9 Paratfins, percent 15.6

The petroleum 'fractions of (2) may be illustrated by a mineral spray oil (Ila) of viscosity 45-80 SUS at 100 F., a viscosity index of 70-80 and having 14.7% aromatics, 85.2% naphthenes and 0.1% parafiins or refined transformer oil and the heavy oils (110) may be illustrated by 150 HVI bright stock, 170 HVI bright stock having a viscosity index of 90-110 or propane asphalt, petroleum resins, asphaltenes, short residues, etc. Oil blends which are particularly useful are:

(A) 60% HVI 100 neutral (In) 30% transformer oil (100 SUS, 100 F., Pl, F.

60, Color NPA 1) 10% unfiltered HVI 150 Bright Stock (VI 95) (B) 60% HVI 100 neutral (Ia) 30% Spray base oil (Ha 45 SUS at 100 F.) 10% unfiltered HVI 150 Bright Stock (C) 95% HVI 100 neutral (Ia) propane asphalt (D) 50% HVI 100 neutral (la) 40% Spray base oil (80 SUS at 100 F.)

Bright Stock (150 neutral) (E) 90% HVI neutral (Ia) 10% transformer oil The compositions of the present invention which contain as the essential additives N-acyl sarcosines and derivatives thereof and alkali metal petroleum sulfonates can be further improved with respect to oxidation stability by addition thereto of from 0.01% to 2%, preferably from 0.1% to 2%, of polymeric ashless dispersants such as nitrogen-containing polymers described in US. Patents 2,737,496, 2,839,512, 2,889,282, 2,944,974, or British 808,665 or polyhdric polymeric compounds described in US. Patents 2,800,450-2. Polymers of this type having a molecular Weight of from 20,000-800,000 can be illu trated by copolymer of lauryl methacrylate/diethylarr1inoethyl methacrylate, copolymer of 2-methyl-5-vinylpyridine/lauryl methacrylate/stearyl methacrylate, copolymer of 2-methyl-5-vinylpyrdine/lauryl methacrylate/stearyl methacrylate/methyl me thacrylate, copolymer of vinyl pyrrolidone/lauryl methcaylate, hydrolyzed copolymer of C1043 alpha-olefin/vinyl acetate. Also desirable is the presence of small amounts (0.1-1%) of phenolic antioxidants such as monoor bisphenols, preferably phenols which contain at least one tertiary alkyl radical. Allryl phenols of this type include 2,4,6-triethyl-, tributyl, trioctyl,

2,4-ditert-butyl-o-methyl,

2,6-ditert-buty1-4-methy1,

2,4,6-ditert-butyl-,

2,6-dicyclohexyl-4-methy1,

2,6-dimethyl-4-cyclohexylphenols,

2,6-ditert-butyl,

2,2-ditert-butyl,

2,6tert-butylcyclohexyl,

2-methyl-6-tert-butyl-4-methylphenols.

The alkyl bisphenols include 1,1-bis-(2-hydroxy-3-tert-butyl-S-methylphenyl) methane;

bis 2-hydroxy-3 -tert-butyl-S-methylphenyl) ethane;

1,1-bis 2-hydroxy-3-tcrt-butyl-S-methylphenyl) propane;

bis( 2-hydroxy-3-tert-butyhS-methylphenyl)butane;

bis (2-hydroxy-3-tert-butyLS-methylphenyl) isobutane;

1,l-bis(2-hydroxy-5-tert-butyl-3-methylphenyl)methane; bis (Z-hydroxy-S-tert-butyl-3-methylphenyl) ethane; 1,1-bis(2-hydroxy-5-tert-butyl-B-methylphenyl)propane; 1, 1 -bis( 2-hydroxy-5-tert-amyl-3-methylphenyl) butane;

1, l-bis 2-hydr0xy-5 -tert-an1yl-3-methylphenyl isobutane; etc. The 2,4,6-trialkyl phenols containing two tertiary alkyl groups in the 2,4- or 2,6-positions are preferred, such as 2,4-ditert-butyl-6-rnethyl-, 2,6flditert-butyl-4-methylphenol or 2,6-ditert-butyl-4-methylolphenol or 4,4-methylene bis (2,6-dibutylphenol) The following compositions illustrates the invention.

Composition I: Percent wt. N-oleoyl sarcosine 0.2 Sodium petroleum sulfonate 0.4 2,6-ditert-butyl-4-methylphenol 0.1 Base oil blend (A) Balance Composition II:

N-oleoylsarcosine 0.25 Sodium petroleum sulfonate 0.4 2,6-di-tert-butyl-4-methylphenol 0.1

Copolymcr of lauryl methacrylate /diethylamine ethyl methacrylate (10) (M.W. 600,000) 0.5 Base oil blend (A) Balance Composition III:

N-oleoyl sarcosine 0.2 Sodium petroleum sulfonate 0.5 Base oil blend (A) Balance Composition IV:

N-oleoyl sarcosine 0.3 Potassium petroleum sulfonate 0.5 Hydrolyzexl copolymer of C1648 alpha-olefin/ vinyl acetate (3:1) (M.W. 27,000) 1 Base oil blend (D) Balance Composition V:

1-hydroxyethyl-Z-heptadecenyl imidazoline N- oleoyl sarcosine 0.2 Sodium petroleum sulfonate 0.4 Base oil blend (A) Balance Composition VI:

Octadecylamine 1 -oleoy1 sarcosine 0.5 Potassium petroleum sulfonate 0.8 Base oil blend (B) Balance Composition VII:

N-lauroyl sarcosine 0.2 Sodium petroleum sulfonate 0.4 2,6-di-tert-butyl-4-methylphenol 0.1 Base oil blend (A) Balance Composition VIII:

N-cocoyl sarcosine 0.3 Calcium petroleum sulfonate 0.5 Hydrolyzed copolymer of C1648 alpha-olefin/ vinyl acetate (3:1) (M.W. 27,000) 1 Base oil blend (D) Balance Composition IX:

1-hydroxyethyl-Z-heptadecenyl imidazoline N- stearoyl sarcosine 0.2 Sodium petroleum sulfonate 0.6 Base oil blend (A) Balance Composition X:

Octadecylamine N-oleoyl sarcosine 0.1 N-oleoyl sarcosine 0.1 Sodium petroleum sulfonate 0.3 Base oil blend (C) Balance The effectiveness of compositions of the present invention as high-speed quenching oils producing excellent surface finishes is demonstrated by testing such compositions as Compositions I, II and V and comparative Composi tion Z (base oil blend A+0.6% sodium petroleum sulfonate) and Composition Y (base oil blend A-l-0.6% N-oleoyl sarcosine) in the General Motors Magnetic Quench Test for Quenching Steel and Quenched Metal all;

Compositions I, II and V was equal to that of Composition Z, or improved by about 15% over Compositiion Y.

Compositions III, IV and VI to X also are excellent quenching speed oils and leave the surface metal clean and bright for further processing.

This application is a continuation-in-part of our copending application Serial No. 64,288, filed October 24, 1960, now US. Patent No. 3,112,232.-

We claim as our invention:

1. A quenching oil composition consisting essentially of a mineral oil blend containing from 0.1 to 2% each of (A) an oil-soluble NC acyl sarcosine and (B) an oil-soluble metal petroleum sulfonate selected from the group consisting of alkali metal petroleum sulfonate and alkaline earth metal petroleum sulfonate, said blend consisting of a predominant amount of a high viscosity index oil having an aromatic content of from 20 to 60% and the balance of the blend being selected from the group consisting of a light oil having a viscosity range of from 40 to 100 SUS at 100 F., a heavy residue fraction having a viscosity of 150-210 and mixtures thereof.

2. The composition of claim 1 wherein the oil blend consists of a mixture of from 50-95% of 80-250 SUS at 100 F. HVI neutral oil having an aromatic content of from 20-60% and the balance being a bright stock.

3. The composition of claim 1 wherein the oil blend consists of a mixture of from 5095% of 80-250 SUS at 100 F. HVI neutral oil having an aromatic content of from 20-60% and the balance being a propane asphalt.

4. The composition of claim 1 wherein the oil blend consists of a mixture of from 50-95% of 80-250 SUS at 100 F. HVI neutral oil having an aromatic content of from 20-60% and the balance being a spray base oil.

5. The composition of claim 1 wherein the oil blend consists of a mixture of from 50-95% of 80-250.SUS at 100 F. HVI neutral oil having an aromatic content 6 of from 20-60% and the balance being a refined transformer oil.

6. A quenching oil composition consisting of a mixture of from -95% of -250 SUS at F. HVI neutral mineral oil having an aromatic content of from 30-60% and the balance being a mixture of bright stock and spray base oil, said mineral oil blend containing from 0.1 to 2% each of N-oleoyl sarcosine and sodium petroleum sulfonate.

7. A quenching oil composition consisting of a mixture of from 50-85% of 80-250 SUS at 100 F. HVI neutral mineral oil having an aromatic content of from 30-60% and the balance being a mixture of bright stock and spray base oil, said mineral oil blend containing from 0.1 to 2% each of octadecyl amine salt of N-oleoyl sarcosine and sodium petroleum sulfonate.

8. A quenching oil composition consisting of a mixture of from 50-85% of 80-250 SUS at 100 F. HVI neutral mineral oil having an aromatic content of from 30-60% and the balance being a mixture of bright stock and spray base oil, said mineral oil blend containing from 0.1 to 2% each of 1-hydroxyethyl-2-heptadecenyl imidazoline salt of N-oleoyl sarcosine and sodium petroleum sulfonate.

9. The composition of claim 6 containing a small amount of a polymeric dispersant and a phenolic antioxidant.

10. The composition of claim 8 containing a small amount of a polymeric dispersant and a phenolic antioxidant.

References Cited by the Examiner UNITED STATES PATENTS 2,536,403 1/51 Wallace et a1. 148-29 2,670,310 2/54 Freeman l4828 2,799,606 7/57 Freeman l4828 3,112,232 11/63 Early et a1. 148-29 BENJAMIN HENKIN, Primary Examiner.

DAVID L. RECK, WINSTON A. DOUGLAS,

Examiners. 

1. A QUENCHING OIL COMPOSITION CONSISTING ESSENTIALLY OF A MINERAL OIL BLEND CONTAINING FROM 0.1 TO 2% EACH OF (A) AN OIL-SOLUBLE N-C10-24 ACYL SARCOSINE AND (B) AN OIL-SOLUBLE METAL PETROLEUM SULFONATE SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL PETROLEUM SULFONATE AND ALKALINE EARTH METAL PETROLEUM SULFONATE, SAID BLEND CONSISTING OF A PREDOMINANT AMOUNT OF A HIGH VISCOSITY INDEX OIL HAVING AN AROMATIC CONTENT OF FROM 20 TO 60% AND THE BALANCE OF THE BLEND USING SELECTED FROM THE GROUP CONSISTING OF A LIGHT OIL HAVING A VISCOSITY RANGE OF FROM 40 TO 100 SUS AT 100*F., A HEAVY RESIDUE FRACTION HAVING A VISCOSITY OF 150-210 AND MIXTURES THEREOF. 